Process of producing tertiary nitriles



Patented Jan. 17, 1933 UNITED STATES PATENT OFFICE MAX BOGKlVIfi'HL Ann ensrnv nnnnnnr,

0F FRANKFORT -ON-THE-MAIN, GERMANY,

ASSIGNORS TO WINT'HROP CI-IEIvIIGAL COMPANY, INC OF NEW YORK, N. Y, A GOR- ZPORATION OF NEW YORK rzaocnss or PRODUCING TERTIARY nrrarnns No Drawing. Application filed December 4, 1931, Serial No. 579,101, and in Germany December 10, 1930;

The present invention relates to a process of producing tertiary nitriles.

In our U. S. Patent No. 1,690,325, dated N.vember 6, 1928, a process of preparing tertiary nitriles is described which consists in treating a secondary nitrile of the general formula bit-0N R/ 5 nitrile thus obtained.

Now we have found that the alkali metal compound of secondary nitriles of the general formula ing to the said process by causing an organic alkali metal compound of the following formula p R-X wherein R stands for alkyl or aryl and X stands for an alkali metal, to act upon the secondary nitrile.

The new process is, for instance, carried out by dissolving or suspending an organic alkali metal compound in a suitable solvent,

e. g. in ether, benzene, ligroine etc., and adding the secondary nitrile to the solutions thus obtained. Hereby a solution of the alkali metal compound of the secondary nitrile is obtained which may then be alkylated according to the known process. I r

It is not necessary to isolate theorganic alkali metal compound before dissolving or suspending it in a solvent. The process may advantageously be carried out by preparing the organic alkali metal compound in the same solution to which the secondary nitrile is to be'added. For instance, sodium ethyl may he prepared from sodium and mercury diethyl in ether, or sodium phenyl may be prepared from sodium and chlorobenzene in benzene, and to the solutions thus obtained the secondary nitrile may be added;

The secondary nitrile may be added after preparing the organic alkali metal. compound or it may be present during its formation. The solutions of the alkali metal compounds of the secondary nitriles thus ob tained may preferably be used immediately for the alkylation .process; the alkylating agent, as for instance, an alkylhalide, may be added to the solutions whereby the alkylation takes place.

The tertiary nitriles-can be prepared according to the present process with a better yield than according to the known process,

as the alkali metal compounds of the sec- 7 ondary nitriles which are to be alkylated are now obtained with a better yield than by causing the alkali metal itself to act upon the secondary nitrile. For instance, according to the process of our U. S. Patent No. 1,690,325 a yield of only about 35% of the theoretical weight of diethylaceto-nitrile-sodium is obtained when causing sodium to act upon. diethylacetonitrile; therefore, when alkylating the product thus obtained, notmore than 35% of alkyldiethylacetonitrile can be obtained. Butvnow according to the new process yields up to 90% of the theoretical weight can be'obtained.

The following examples illustrate our invention. T

(1) 2.5 grams of sodium in the form of wire are covered with 150 cc. of dry ether and 15 grams of diethyl mercury are added drop by drop. Then 11.3 grams of diethyl-' acetonitrile are added drop by drop, whereupon a very lively reaction sets in. After an hours stirring 8.3 grams of allyl chloride are added drop by drop, the very lively reaction being moderated by cooling. The reaction product is poured into ice water and the wire) are covered with 100 cc. of benzene and 23 grains of butylchloride are introduced,

drop by drop, at C. to C. in a nitrogen atmosphere. After the course of 4 to 5 hours nearly all of the sodium is consumed. 24 grams of diethylacetonitrile are then introduced drop by drop, at 0 C.- C. After introduction of the Whole quantity and stirring for 1 hour at room temperature, 19 grams of allyl chloride are introduced drop by drop, while strongly cooling. The Whole is finally boiled for hour in a reflux apparatus. The reaction product is poured into water, the aqueous portion is separated and again extracted with ether. The ethereal extract is combined with the benzene extract and dried; the etherand benzene are distilled offand the residue is distilled in a vacuum. Diethylallylacetonitrile is obtained; it boils at 79 C. to 81 C. under 20 mm. pressure.

(3) On 11.5 grams of sodium (in the form of wire) there are poured 125 cc. of benzene and 28 grams of chlorobenzene are added. The reaction sets in after about hour, but the temperature must preferably not exceed 30 0. As soon as the reaction is complete, 24 grams of diethylacetonitrile are introduced drop by drop, but the temperature must preferably not be above 20 C. to 30 C. After introduction of the whole quantity and stirring for 1 hour at room temperature, 18 grams of allyl chloride are added while strongly cooling. After the product has been Worked up as described in Example 2, 31 grams of diethylallylacetonitrile are obtained. i I

(4)16 grams of sodium and '41 grams of chlorobenzene are causedto react in a mixture of 100 cc. of benzene and 100 cc. of ligroin (boiling, at C. to 80C.) as described in Example 3. 30 grams of diallylacetonitrile are then introduced, drop by drop, while cooling. 7 The whole is preferably stirred for 1 hour. Then 26.5 grams of isoamyl chloride are introduced. The product is worked up as indicated in Example 3. 38 grams of diallylisoamylacetonitrile are obtained. It boils at 109 C. to 110 C. under 7 mm.

pressure.

(5) 11.5 grams of sodium and 30 grams of chlorobenzene are caused to react in 120 cc. of benzene as described in Example 3 and mixed first with 21'grams of ethylallylacctonitrile and then with 14.5 grams of allyl chloride. 21 :grams of ethyldiallylacetonitrile.

are obtained; it boils at 83 C. to 85 C. under 13 mm. pressure.

(6) 11.5 grams of sodium and 30 grams of chlo-robenzene are caused to react in 120 cc. of benzene as described in Example 3 and mixed in succession with 25 grams of butylethylacetonitrile and 15.5 grams of allyl chloride. 28 grams of ethyl-butyLallylacetonitrile are obtained; it boils at C. to 77 C. under 2 to 3 mm. pressure.

(7) 16.0 grams of sodium and 41 grams of chlorobenzene are caused to react in a mix ture of 100 cc. of benzene and 100 cc. of ligroin (boiling at 50 C. to C.) as described in Example 3 and mixed in successionwith 34' grams of diallylacetonitrile and 21.5 grams v of allyl chloride. 40 grams of tria-llylacetonitrile are obtained. It boils at 86 C. to

Whenthe reaction is complete, the whole is v stirred for 4 to 6 hours at room temperature and-59 grams of allyl chloride are then'intro-- duced, drop by drop, while cooling. Finally the whole is heated for hour to 60 (lit is then poured into water, separated and the aqueous portion is again shaken with benzone; the benzene solution is washed with Water, dried by way of sodium sulfate, the benzone is distilled oif and the residue is distilled in avacuum. The diethylallylacetonitrile dis tills over at 76 O.to 78 (lunder 14 mm. pressure. The yield amounts to 90 grams.

(9) 46 grams of sodiumare covered-with 400 cc. of benzene and a mixture'of 120 grams of chlorobenzene and 75 grams of diethylacetonitrile is introduced, drop by drop',"the whole being cooled in such a mannerthat the reaction temperature does not exceed 20 to 25 C. After the reaction is complete, the whole is stirred for 4 to 5 hours and 59 grams of allyl chloride are introduced, drop by drop, while cooling. The productis worked up as indicated in Example 8. 90 grams of dicthylallylacetonitrile are obtained.

(10) 11.5 grams ofsod'um are covered With 120 cc. of benzene and a mixture of 30 grams of chlorobenzene and 21 grams of ethylallyl acetonitrile is introduced by drops, the whole being cooled in such a manner that the temperature does not exceed 20 C. to 25 C. The whole is then stirred for4 to 5 hours and 14.5 grams of allyl chloride areintroduced by drops. After having Worked up the prodtained 25 grams of ethyldiallylacetonitrile. Tt boils at 83 C. to 85 C. under 13 mm. pressure. a

(11) 16 grams of sodium are covered with 100 cc. of benzene as described in Example 10 and a mixture of 34 grams of diallyl'acetonitrile and 41 grams of chlo-robenzene is run in. The whole is then mixed with 21.5 grams of allyl chloride. The product is worked up as indicated in Example 8. 41 grams of, triallylacetonitrile are' obtained; it boils at 86 C. to 88 C. under 8 to 9 mm. pressure. 7

(12) 11.5 grams of sodium,120 cc. of benzene, 29 grams of chlorobenzeneand 18-grams of diethylacetonitrile are mixed together and stirred. The very lively reaction which sets in after a short time is moderated by cooling. After 2 to 3 hours 14 grams of allyl chloride are introduced by drops and the whole is worked as indicated in Example 8. 16 grams of diethylallylacetonitrile are obtained.

(13) 11.5 grams of sodium, 120 cc. of benzene and 18 grams of diethylacetonitrile are mixed and 29 grams of chlorobenzene are in troduced at 20 C. to 30 G. into the mixture.

After the reaction is complete, 14.5 grams of wherein R stands for alkyl or alkenyl, into the corresponding alkali metal compound and causing an alkylating agent to act upon the alkali metal compound of the secondary nitrile, the step which comprises preparing the alkali metal compound of the secondary nitrile by causing an organic alkali metal compound of the general formula wherein It stands for alkyl or aryl and X stands for an alkali metal, to act in the presence of a solvent upon the secondary nitrile.

2. In the process of preparing teritiary nitriles by transforming a secondary nitrile of the general formula EH-ON wherein R stands for alkyl or alkenyl, into the corresponding alkali metal compound and causing an alkylating agent to act upon the alkali metal compound of the secondary nitrile, the step which comprises preparingthe alkali metal compound of the secondary nitrile by causing an organic alkali metal compound of the general formula whereinR stands for ethyl or phenyl and X stands for an alkali metal to act in the presence of an organic solvent upon the secondary nitrile.

3. In the process of preparing tertiary nitriles by transforming a secondary nitrile of the general formula Eli-ON wherein R stands for alkyl or alkenyl into the corresponding sodium compound and causing an alkylating agent to act upon the sodium compound of the secondarynitrile, the step which comprises preparing the sodium compound of the secondary nitrile by causing sodium phenyl to act in the presence of an organic solvent upon the secondary nitrile.

4. In the process of preparing tertiary nitriles by transforming a secondary nitrile of the general formula wherein R stands for alkyl or alkenyl into the corresponding sodium compound and causing an alkylating agent to act upon the sodium compound of the secondary nitrile, the step which comprises preparing the sodium compound of the secondary nitrile by causing sodium phenyl to act in the presence of benzene upon the secondary nitrile.

5. In the process of preparing tertiary nitriles by transforming the secondary nitrile of the formula CH-ON into the corresponding sodium compound and causing an alkylating agent to act upon the sodium compound of the secondary nitrile, the step which comprises preparing the sodium compound of the secondary nitrile by causing sodium phenyl to act in the presence of benzene'upon the secondary nitrile.

In testimony whereof, we affix our signatures.

MAX BOCKMIIHL. GUSTAV EHRHART. 

